Protecting-group-directed stereodivergent Tsuji–Trost cyclization: total synthesis of oxylipids and (+)-petromyroxol

Abstract

A stereodivergent protecting-group-directed Tsuji–Trost cyclization for efficient synthesis of both 2,5-cis- and 2,5-trans-disubstituted-THF scaffolds has been realized. The presence of a β-O-silyl group in allyl acetate results in cis-2,5-disubstituted-3-oxygenated THF in a good up to 9 : 1 dr. Alternatively, when the free OH at the β-position is available for acetate co-ordination, it gives a trans-2,5-disubstituted-3-hydroxy THF scaffold almost as a single diastereomer (up to 1 : 0 dr). The THF scaffolds synthesized were carried forward in the total synthesis of oxylipids and (+)-petromyroxol.